CN102744039B - A kind of porous active storage ammonia active mixture preparation containing clay - Google Patents
A kind of porous active storage ammonia active mixture preparation containing clay Download PDFInfo
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- CN102744039B CN102744039B CN201210238823.9A CN201210238823A CN102744039B CN 102744039 B CN102744039 B CN 102744039B CN 201210238823 A CN201210238823 A CN 201210238823A CN 102744039 B CN102744039 B CN 102744039B
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 210
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 105
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 238000003860 storage Methods 0.000 title claims abstract description 34
- 239000004927 clay Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical class [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000013019 agitation Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims abstract description 3
- 230000009514 concussion Effects 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000010427 ball clay Substances 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000012512 characterization method Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 238000011049 filling Methods 0.000 description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000003795 desorption Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000446 fuel Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000011343 solid material Substances 0.000 description 7
- 239000004202 carbamide Substances 0.000 description 6
- 235000013877 carbamide Nutrition 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000003368 amide group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- -1 amino borane compound Chemical class 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000008280 blood Substances 0.000 description 3
- 210000004369 blood Anatomy 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000013467 fragmentation Methods 0.000 description 3
- 238000006062 fragmentation reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 108010033040 Histones Proteins 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 210000000795 conjunctiva Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011217 control strategy Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000002405 diagnostic procedure Methods 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 238000007907 direct compression Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Fuel Cell (AREA)
Abstract
The present invention relates to a kind of porous active storage ammonia mixture preparation containing clay, it is characterized in that: the powder adopting the anhydrous calcium chloride salt of industry, mix appropriate clay, active carbon, deionized water and industrial alcohol, the Homogeneous phase mixing wet feed of mechanical agitation furnishing semi-drying, be filled in tank body, make Integrate porous solid block, ammonia conveying hole in this solid block is enriched, macroscopically possess some macropores, possess and fill ammonia faster and store up ammonia performance preferably, ammonia can be discharged fast, can recycle not broken, possess efficient adsorption and conciliate characterization of adsorption, be applicable to the adsorption storage of ammonia, for SCR and FCEV system, meet the application demand of future automobile industry.
Description
Technical field
The present invention relates to a kind of porous active storage ammonia active mixture preparation containing clay, be particularly applied to SCR aftertreatment system and the FCEV fuel cell system of vehicle exhaust.
Background technology
Current, the whole world faces the integration challenges of the energy and environment, and in the technological means selection of the emission compliance of orthodox car, and the fuel supply technical elements people of new-energy automobile still face many difficult problems.
SCR aftertreatment system relies on the accurate supply of carbamide reducing agent and resolves into ammonia De NO X hazardous material afterwards in the front end of catalyst, reach the object of cleaning of off-gas, the standard of the state 4 realizing vehicle or more up to standard, but, in actual use, this dependence urea decomposition becomes the metered injection of the liquid area of ammonia to there is many deficiencies and difficult point, such as, the problem of urea liquid icing blocking under-11 DEG C of environment, needs extra pipeline heating system to solve, could decompose under the temperature environment of urea liquid more than 135 DEG C, and many vehicles of public transit system loiter, urea liquid stable decomposition temperature cannot be reached at all, cannot output ammonia, predetermined NOX composition cannot be eliminated, finally cause the accumulation of liquid area in blast pipe, produce the polymer of melamine, blocking urea nozzle and the exhaust pipe of engine, vehicle is caused to produce fault, impact is normal to be used, in addition, if the main flow vehicle of state more than 4 uses SCR system comprehensively, relate to the problem of about 150,000, whole nation oiling website Innovation Construction liquid area filling infrastructure, huge owing to investing, still do not see that Government and enterprise starts to improve this infrastructure at present, become SCR use in a potential huge problem,
For breakthrough energy dilemmas, solve the new-energy automobile development problem of future source of energy problem, it is a very important technology path that hydrogen fuel cell is recognized, but, how stable acquisition hydrogen source is a no small difficult problem for restriction this area development, likely in adopted hydrogen source mode, gas cylinder is had to store up the technology path of hydrogen, there is the technology path of water electrolysis hydrogen production, there is the technology path of high-purity hydrocarbon petroleum fuels cracking hydrogen production, the presoma decomposition of the technology path of low molecule alcohols cracking hydrogen production and the hydrogeneous of other H-N or the technology path of cracking hydrogen production, in above-mentioned technology path, all there is some problem and deficiency, such as, hydrogen production efficiency and cost, hydrogen manufacturing precision and speed, also the problem of system aspects is comprised, in a word, the source of hydrogen is the bottleneck of fuel-cell vehicle development, people's idea is needed to solve,
The presoma of hydrogen one of them be the hydrogeneous compound of H-N, wherein, what hydrogen-storage density was the highest is ammonia.Ammonia is a kind of modal industrial chemicals, and ammonia molecule belongs to active polar molecule, and the diameter dimension of molecule is about 3 ~ 4A, and therefore, very active under normal temperature, very easily spreads, and have toxic, its toxic is embodied in has corrosion and spread effect to the skin histology of contact, can absorb the moisture in skin histology, make histone sex change, and make tissue fat saponification, destroys membrane structure, ammonia in water solubility high, so mainly have stimulation and corrosiveness to the upper respiratory tract of animal or human's body, often be attracted on mucocutaneous and eye conjunctiva, thus produce stimulation and inflammation, in addition, ammonia sucks human body usually in gaseous form, easily blood is entered by alveolar after ammonia is inhaled into lung, be combined with hemoglobin, destroy fortune oxygen function, enter IA ammonia, small part is neutralized by carbon dioxide, remainder is absorbed into blood, there will be after sucking a large amount of ammonia in a short time and shed tears, pharyngalgia, cough, uncomfortable in chest, expiratory dyspnea, dizzy, vomiting, weak etc., if the long-term ammonia sucked is too much, cause ammonia density in blood too high, will cause heart stop fight and breathe stopping, threat to life safety, therefore, the maximum hidden danger of the use of ammonia is safety problem.
As can be seen here, resolve in the use of ammonia and store and safety problem, just can open up the technology path of a new ammonia utilization.
Traditional ammonia storing mode is gas cylinder, or realizes with the water-soluble formation ammoniacal liquor of high concentration ammonia.If adopt gas cylinder to store ammonia, there is the potential safety hazard of operating aspect and seal aspect in commercial Application in enormous quantities, if in the mode of high concentrated ammonia liquor, there is again serious etching problem.
At China national patent information net, to be the theme word and search to store up ammonia, ' composite functional ammonia storage device ' that the patent No. is ' a kind of Urotropine tail gas ammonia recovery device with gas phase method ' of CN201120099229.7, the patent No. is CN201020677361.7 ' the Pei An bindiny mechanism for machine room of refrigerated warehouse ', the patent No. are CN201020269811.9, the patent No. are ' a kind of ammonia steaming device ' of CN200520057558.X, be that a class carries out to ammonia nitrogen industrial wastewater the environment protection treating device that ammonia nitrogen gets rid of process, also do not relate to the characteristic component in the present invention.Uncorrelated with the present invention;
These 2 inventions of number of patent application to be ' method and system for testing to the work of SCR catalyst ' of CN201010244091.5 and number of patent application be ' operation method of SCR exhaust after treatment system and the diagnostic method ' of CN200880104697.X provide a kind of for SCR (SCR) catalytic converter and traditional liquid ureaclastic ammonia dispensing module and control system, do not relate to the characteristic component of compound;
Number of patent application is that the invention of ' a kind of preparation method of efficient low-temperature ammonia-storing material ' of CN200910197860.8 is applied to SCR aftertreatment system, feature is that amino borane compound is placed in closed container, vacuumize, at 0-4 DEG C of temperature, contact with ammonia, at 0-4 DEG C of temperature, keep 30-60 minute, prepare required product amino borane ammino-complex NH
3bH
3(NH
3) n (n=1-3); The maximum storage ammonia amount of room temperature can reach 62.4wt.%, room temperature supply gas pressure about 2.0bar, room temperature is moderate for ammonia pressure, ammonia completely reversibility is put in suction, but the extraordinary material amino borane of this patent is expensive, there is higher explosion danger and burning grade, be not suitable for applying in enormous quantities of general industry field;
Number of patent application is that the invention of the solid material of delivering ammonia ' store and ' of CN200580026626.9 relates to and storing and the solid material of delivering ammonia.The solid material of this storage ammonia comprises a kind of ammonia and absorbs salt, and wherein this ammonia absorption salt is general formula is M
a(NH
3)
nx
zionic salt, wherein M is one or more cations being selected from alkaline-earth metal and/or one or more transition metal such as Mn, Fe, Co, Ni, Cu and/or Zn, X is one or more anion, a is the cation number that each molecules of salt comprises, z is the anion number that each molecules of salt comprises, n is the ligancy of 2 ~ 12, and wherein M is Mg, and it is that auto industry ammonia provides a kind of safety, lightweight, cheap and fine and close storage that this ammonia absorbs salt.This patent is that electric heating adds Thermal desorption ammonia direct for solid material compression molding, more lays particular emphasis on the control strategy of system, does not relate to modification and the optimization of mixture;
The patent No. is that ' purposes of ammonia storage device in energy production ' invention of CN200580009219.7 relates to a kind of generator unit, and this unit comprises the ammonia storage device of (i) container (2) form, and comprising general formula is M
a(NH
3)
nXzammonia absorb with release salt, wherein M is one or more cations, be selected from alkali metal, alkaline-earth metal and transition metal are as Li, K, Mg, Ca, V, Cr, Mn, Fe, Co, Ni, Cu or Zn, X is one or more anion, be selected from fluorine root, chlorine root, bromine root, iodine root, nitrate anion, thiocyanate radical, sulfate radical, molybdate, phosphate radical and chloranion, a is the cation number of each molecules of salt, z is the anion number of each molecules of salt, and n is the ligancy of 2-12, (ii) for heating described container (2) and ammonia absorption and release salt to discharge the device (3a) of ammonia, (iiia) for ammonia being converted into the fuel cell of electrical power, or (iiib1) for ammonia being dissociated into the reactor (6) of hydrogen and nitrogen, (iiib2) for hydrogen being converted into the fuel cell (4) of electrical power, this patent is mainly used in fuel cell, refer to property material in claim 4 for such salt or be positioned on porous carrier materials, which kind of material statement is not,
A kind of amido complex compound of the disclosure of the invention of CN200710156866.1 ' a kind of amido complex compound and its production and use ' and its production and use.The composition of this amido complex compound is MX
m(NH
3)
n, in formula, M is one or more in Li, Mg, Al, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Ba, Sn; X is F, Cl, Br, NO
3, SO
4in one or more; M determines according to chemical valence, 1≤m≤5; N determines according to ligancy, 1≤n≤15.Using the amido complex compound after deamination as the absorbent of ammonia, inhale ammonia by low temperature, high temperature puts ammonia and realize the separation of ammonia, purification, storage and transport.This patent only relates to preparation technology and the process of this amido complex compound itself;
Number of patent application is that the solid ammonia that ' high-density city of ammonia ' patent of CN200680005886.2 comprises ammonia absorption/desorption solid material stores and conveying material, the described density that has been compacted to is greater than the storage of 50% of theoretic skeleton density and carries material to provide solid ammonia storage material, this storage medium is easily prepared and is processed and have the storage ammonia of very high-density, described storage ammonia easily discharges under controlled conditions, even if the porosity of described material is very low still like this, and this storage medium is safe for storage and delivering ammonia, do not need special safety measure.This patent adopts the direct compression molding of solid material, adopt binding agent, only stating may be silicon dioxide fibre binding agent, not dosage ratio, also only state that solid material may comprise granular materials, porous material, crystalline material, amorphous materials or their bond composition in other claim and embodiment, do not have the thin item of clear and definite claim, industry technology personage almost cannot implement.Create the present invention therefrom.
Summary of the invention
The object of the present invention is to provide a kind of porous active to store up the preparation of ammonia active mixture, it improves the hole of storage ammonia active material solid block effectively, increases ammonia transmission channel, weakens or avoid repeatedly CaCl in sorption and desorption additive process
2the efflorescence fragmentation of the caking occurred and solid block, what meet industrial occasions repeatedly recycles requirement.
Technical scheme of the present invention is achieved in that the preparation of a kind of porous active storage ammonia active mixture, it is characterized in that concrete preparation method is as follows: the powder by mass fraction being the anhydrous calcium chloride salt of industry of 45 ~ 92 parts, mix the industrial ball clay of 1 ~ 15 part, 2 ~ 8 parts of active carbons, with the deionized water of 3 ~ 17 parts and the industrial alcohol of 2 ~ 15 parts, mechanical agitation is mixture wet feed uniformly, be filled in tank body, addition is no more than 80% of tank volume, and machinery concussion 5 ~ 10min eliminates the air gap; Whole tank body is put in vacuum drying oven, slowly heat under normal pressure, temperature controls at 65 ~ 160 DEG C, eliminating water and ethanol are to mixture constant weight, substep is evacuated to 550mbar, constant temperature and pressure 0.5 ~ 3h, takes out tank body, sealing charge door, makes the storage ammonia active mixture Integrate porous solid block containing clay; Ammonia is filled with in tank body under 0.05 ~ 0.8MPa pressure, saturated to mixture absorbing ammonia.
The clay particle diameter of described industrial ball clay is less than 2um, and in water, disperse becomes suspension.
Described activated carbon pore size distribution is greater than 800m at 2 ~ 50nm, specific surface
2/ g.
Described tank body is the withstand voltage tank body of stainless steel, inner tank wall thermal spraying nylon heat-insulation layer.
Good effect of the present invention is the activity storage ammonia mixture that the ammonia conveying hole containing clay is abundant, ensure that under the prerequisite that storage ammonia active material characteristic is constant, the clay added and active carbon weaken or avoid the phenomenon of the ammonia gas absorption desorption that caking, fragmentation etc. cause, improve the richness of microscopic void, add the quantity of macroscopic pores, improve the mechanical strength of mixture solid block, there is very high practical value, be suitable for SCR post processing or the FCEV system of automobile industry.By means of mechanical agitation and CaC1
2and other fillers fully mix, at CaC1
2bridging between particle, forms mechanical strength higher " integrated solid block " after dry, can effectively weaken or avoid the efflorescence fragmentation that the dilation of solid block in sorption and desorption additive process causes; The water added and ethanol dissolve and differential falls apart CaC1
2and other fillers, improve the wetting and spreading between liquid-solid two-phase, in addition, the hole that process is formed deviate from by water and ethanol, enriched the transmission channel of ammonia; The active carbon added facilitates CaC1
2dispersion, can effectively weaken or avoid the generation of caking phenomenon, improve the richness of microscopic void, add the transmission channel of ammonia, greatly improve the permeance property of ammonia, promote the formation of ammino calcium chloride complex compound, the loose structure of active carbon itself, possesses certain absorption and memory function to ammonia simultaneously; The activated carbon pore size distribution herein selected is greater than 800m at 2 ~ 50nm, specific surface
2/ g; In order to ensure security at elevated pressures.
Accompanying drawing explanation
The thermogravimetric curve figure of the active mixture of the absorbing ammonia of Fig. 1 embodiment of the present invention 1.
Detailed description of the invention
Further describe the present invention below by embodiment, embodiment, for illustrate feature of the present invention further, is not equal to restriction the present invention, for the change that those skilled in the art carries out according to the present invention, all should be included within protection scope of the present invention.
embodiment 1
By the water of mass fraction by the calcium chloride of 71 parts, 3 parts of active carbons, 6 parts of clays and 12 parts, 1h is mixed in homogenizer, add 8 parts of ethanol, continue mechanical agitation 3h, make uniform mixture wet feed, be filled in tank body, be added into 80% of tank volume, machinery concussion 10min eliminates the air gap;
Whole tank body is put in vacuum drying oven, rises to 120 DEG C as shown in Figure 1 under normal pressure with the heating rate of 2 DEG C/min, constant temperature 6h, get rid of water and ethanol, substep is evacuated to 550mbar, constant temperature and pressure 1h, take out tank body, sealing charge door, make storage ammonia active mixture Integrate porous solid block.
embodiment 2
By the water of 2 parts of active carbons, 15 parts of clays and 15 parts, 1h is mixed in homogenizer, add the calcium chloride mixing 1h of 58 parts, add 10 parts of ethanol, continue mechanical agitation 3h, make uniform mixture wet feed, be filled in tank body, be added into 75% of tank volume, machinery concussion 10min eliminates the air gap;
Whole tank body is put in vacuum drying oven, rises to 120 DEG C under normal pressure with the heating rate of 2 DEG C/min, constant temperature 6h, get rid of water and ethanol, substep is evacuated to 550mbar, constant temperature and pressure 1h, take out tank body, sealing charge door, make storage ammonia active mixture Integrate porous solid block.
embodiment 3
By the water of 5 parts of clays and 6 parts, 1h is mixed in homogenizer, add the calcium chloride mixing 1h of 80 parts, add 3 parts of active carbon mixing 1h, add 6 parts of ethanol, continue mechanical agitation 3h, make uniform mixture wet feed, be filled in tank body, be added into 80% of tank volume, machinery concussion 10min eliminates the air gap;
Whole tank body is put in vacuum drying oven, rises to 100 DEG C under normal pressure with the heating rate of 5 DEG C/min, constant temperature 8h, get rid of water and ethanol, substep is evacuated to 550mbar, constant temperature and pressure 2h, take out tank body, sealing charge door, make storage ammonia active mixture Integrate porous solid block.
embodiment 4
The tank body that the storage ammonia active mixture completed for embodiment 1 installs additional, adopt high-purity industrial ammonia bottle by pipe valve for subsequent use, slowly carry out filling ammonia in the inlet pressure ranges of 0.4Mpa, filling the ammonia time is 3h, and filling tank body quality before and after ammonia increases by 38%;
Complete the tank body after filling ammonia to be connected with automobile SCR system, when NH_3 leakage amount is less than 10ppm, Mass lost 33% before and after test tank body desorption.
embodiment 5
The tank body that the storage ammonia active mixture completed for embodiment 2 installs additional, adopt high-purity industrial ammonia bottle by pipe valve for subsequent use, slowly carry out filling ammonia in the inlet pressure ranges of 0.2Mpa, filling the ammonia time is 6h, and filling tank body quality before and after ammonia increases by 33%;
Complete the tank body after filling ammonia to be connected with automobile SCR system, when NH_3 leakage amount is less than 10ppm, Mass lost 30% before and after test tank body desorption.
embodiment 6
The tank body that the storage ammonia active mixture completed for embodiment 3 installs additional, adopt high-purity industrial ammonia bottle by pipe valve for subsequent use, slowly carry out filling ammonia in the inlet pressure ranges of 0.5Mpa, filling the ammonia time is 5h, and filling tank body quality before and after ammonia increases by 40%;
Complete the tank body after filling ammonia to be connected with automobile SCR system, when NH_3 leakage amount is less than 10ppm, Mass lost 36% before and after test tank body desorption.
Claims (3)
1. the porous active storage ammonia active mixture preparation containing clay, it is characterized in that preparation method is as follows: the powder by mass fraction being the anhydrous calcium chloride salt of industry of 45 ~ 92 parts, mix industrial ball clay, 2 ~ 8 parts of active carbons that 1 ~ 15 part of particle diameter is less than 2um, with the deionized water of 3 ~ 17 parts and the industrial alcohol of 2 ~ 15 parts, mechanical agitation is mixture wet feed uniformly, be filled in tank body, addition is no more than 80% of tank volume, and machinery concussion 5 ~ 10min eliminates the air gap; Whole tank body is put in vacuum drying oven, slowly heat under normal pressure, temperature controls at 65 ~ 160 DEG C, eliminating water and ethanol are to mixture constant weight, substep is evacuated to 550mbar, constant temperature and pressure 0.5 ~ 3h, takes out tank body, sealing charge door, makes the storage ammonia active mixture Integrate porous solid block containing clay; In tank body, ammonia is filled with under 0.05 ~ 0.8MPa pressure, saturated to mixture absorbing ammonia.
2. a kind of porous active storage ammonia active mixture preparation containing clay according to claim 1, is characterized in that described industrial ball clay disperse in water becomes suspension.
3. a kind of porous active storage ammonia active mixture preparation containing clay according to claim 1, is characterized in that described activated carbon pore size distribution is greater than 800m at 2 ~ 50nm, specific surface
2/ g.
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| CN113069874B (en) * | 2021-03-31 | 2022-11-29 | 中钢集团鞍山热能研究院有限公司 | Treatment system and process suitable for VOCs in chemical production area of coking plant |
| CN116617806B (en) * | 2023-05-23 | 2023-11-03 | 迁安市宏奥工贸有限公司 | Method for treating waste gas of coking plant |
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